US4147868A - Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions - Google Patents
Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions Download PDFInfo
- Publication number
- US4147868A US4147868A US05/870,705 US87070578A US4147868A US 4147868 A US4147868 A US 4147868A US 87070578 A US87070578 A US 87070578A US 4147868 A US4147868 A US 4147868A
- Authority
- US
- United States
- Prior art keywords
- acetylene
- oligomer
- bis
- mole
- quinoxaline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/36—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems
- C07D241/38—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings condensed with carbocyclic rings or ring systems with only hydrogen or carbon atoms directly attached to the ring nitrogen atoms
- C07D241/40—Benzopyrazines
- C07D241/42—Benzopyrazines with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0683—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0694—Polycondensates containing six-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring, e.g. polyquinoxalines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Acetylene-terminated quinoxaline compositions are prepared by reacting an aromatic bisbenzil with an excess of a bis(o-diamine) to provide an ortho-diamino endcapped quinoxaline oligomer which is then converted to the acetylene endcapped composition by reacting with an acetylenic benzil.
Description
The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.
This is a division of application Ser. No. 762,078, filed Jan. 24, 1977, and issued on July 4, 1978, as U.S. Pat. No. 4,098,825.
This invention relates to acetylene-substituted aromatic benzils and to a method for their preparation. In one aspect, it relates to acetylene-terminated quinoxaline compositions.
The acetylene-terminated polyphenylquinoxalines, disclosed in U.S. Pat. No. 3,966,729, are one of the most promising new matrix resins for advanced aircraft and aerospace systems. The materials propagate and cure by addition reactions to form high molecular weight, thermally stable compositions. The addition process obviates all problems associated with volatile by-product formation that occurs when such materials are prepared by the normal condensation process. The new resins demonstrate an excellent potential for use as matrices in high performance structural composites.
The principal drawback in the acetylene-terminated quinoxaline system disclosed in the aforementioned patent is the difficulty in working with the very unstable 4-(3-ethynylphenoxy)orthophenylene diamine utilized as the oligomer endcapping agent. Because of the susceptibility of the endcapping agent to oxidation, it cannot be isolated and stored for any length of time. As a result, the resins prepared with the agent are very costly, an important factor in selecting resins for use as composite matrices.
It is a principal object of this invention, therefore, to provide improved acetylene-containing endcapping agents that overcome the shortcomings of the agent disclosed in the aforementioned patent.
Another object of the invention is to provide a process for preparing the acetylene-containing endcapping agents.
A further object of the invention is to provide improved acetylene-terminated phenylquinoxaline oligomers which exhibit low softening points, thereby making such materials more amenable to composite fabrication.
Still another object of the invention is to provide a process for preparing the acetylene-terminated phenylquinoxaline oligomers.
Other objects and advantages of the invention will become apparent to those skilled in the art upon consideration of the ensuing disclosure.
The present invention resides in acetylene-substituted aromatic benzils as represented by the following formula: ##STR1## wherein R is oxygen or sulfur and R is ortho, meta or para to the carbonyl functionality.
The acetylene-containing aromatic benzils having the foregoing formula are prepared by the nucleophilic displacement reaction of a nitro leaving group of a benzil (IV) with a metallic salt of an ethynyl-substituted phenol or thiophenol (III). The metallic salt is generated from the base hydrolysis of the corresponding tosylated phenol or thiophenol (II). The reactions involved are shown by the equations set forth below in which the Roman numerals refer to the compounds indicated in the preceding sentences and the Roman number (I) designates the acetylene-containing aromatic benzils. ##STR2## In the above equations, Tos is ##STR3## R is oxygen or sulfur, and M is an alkali metal, such as potassium or sodium. The materials used in synthesizing the acetylenic benzils (I) are well known compounds that are described in the literature. The acetylenic benzils are stable to both air and light so that they have a long shelf life. As a result the compounds are amenable to commercial production in a scaled-up process.
In one embodiment, the instant invention resides in acetylene-terminated quinoxaline compositions which cure by non-volatile addition reactions. The quinoxaline compositions are prepared by reacting an aromatic bisbenzil (V) with an excess of a bis(o-diamine) (VI), thereby providing an ortho-diamino endcapped quinoxaline oligomer (VII) which is then converted to the acetylene endcapped oligomer (VIII) by reacting with an acetylenic benzil (I). The reactions that occur are shown below by the equations in which the Roman numerals refer to the compositions mentioned in the preceding sentence. ##STR4##
In the foregoing formulas, X is a single bond, --O--, --S--, ##STR5## and R is as indicated above. The letter n is an integer indicating the number of recurring units and is usually in the range of 1 to 20, inclusive.
The bis(o-diamines) and the aromatic bisbenzils utilized in preparing the quinoxaline compositions are well known compounds that are described in the literature. Examples of bis(o-diamines) include 3,3'-diaminobenzidine; 3,3', 4,4'-tetraaminodiphenylether; 3,3', 4,4'-tetraaminodiphenylsulfide; 3,3', 4,4'-tetraaminodiphenylsulfone; 3,3'-4,4'-tetraaminodiphenylmethane; 3,3', 4,4'-tetraaminobenzophenone; 1,3-bis(3,4-diaminophenoxy)benzene; and 2,2'-bis(3,4-diaminophenoxy)-giphenyl. Examples of aromatic bisbenzils include 4,4'-(phenylglyoxaloyl)diphenylether; 1,3-(phenylglyoxaloyl)benzene; 4,4'-(phenylglyoxaloyl)diphenylsulfide; 1,3-bis(4-phenoxyphenylglyoxaloyl)benzene; and 1,4-bis[4-(phenylglyoxaloyl)phenoxy]benzene.
As indicated above, in the first step of preparing the acetylene-terminated quinixaline compositions, an aromatic bisbenzil is reacted with an excess of a bis(o-diamine). Usually, from about 0.10 to 1 mole of the bis(o-diamine) is reacted with 2 moles of the bisbenzil. When the mole ratio of bis(benzil) to bis(o-diamine) is 2 to 1, the value of n in the above equation is 1. As the ratio increases, i.e., greater amounts of bisbenzil as compared to bis(o-diamine) are used, the value of n in the equation also increases. The number of moles of acetylenic benzil endcapping agent used in the second step of the process is generally about equal to the number of moles of the bis(o-diamine) utilized in the first step. It is within the purview of the inventin, however, to employ a molar excess of the endcapping agent, e.g., 1 to 1.25 moles of endcapping agent per mole of bis(o-diamine).
In conducting the process, m-cresol is employed as the reaction medium. The amount of m-cresol used is that which is sufficient to provide a stirrable mixture and can be readily determined by those skilled in the art. The temperatures at which the reactions are carried out usually fall in the range of 80° to 150° C. The total period for the reactions generally ranges from about 30 minutes to 4 hours. The reactions are conducted under a blanket of an inert gas, such as nitrogen, argon or helium.
At the end of the reaction period, the oligomer is recovered and purified by a general procedure that is conventionally followed in solution polymerization processes. Thus, the reaction mixture is cooled, e.g., to about room temperature, after which it is poured into a non-solvent for the oligomer, thereby causing it to precipitate from solution. An alcohol, such as methanol, is conveniently used as the non-solvent. The precipitated oligomer is separated from the liquid by any suitable means, such as by filtration or decantation. After washing the separated oligomer with a non-solvent, it is then dissolved in a solvent, such as tetrahydrofuran, and again precipitated from solution by pouring into a non-solvent. After separation of the precipitated oligomer, it is dried by heating under a vacuum. This procedure can be repeated one or more times in order to further purify the product.
The acetylene-terminated quinoxaline oligomers are readily cured by heating in an inert or oxidative atmosphere at a temperature ranging from about 200° to 370° C. A heating period of from about 1 to 2 hours is usually sufficient to obtain a complete cure. However, longer times, e.g., up to 24 hours, can be used.
A more complete understanding of the invention can be obtained by referring to the following illustrative examples which are not intended, however, to be unduly limitative of the invention.
To 100 ml of anhydrous methanol was added 20 g (0.073 mole) of 3-ethynylphenyl(p-toluenesulfonate) and 8.19 g (0.146 mole) of potassium hydroxide. The mixture was heated to reflux under a nitrogen atmosphere and maintained at reflux for 4 hours. A distillation apparatus was attached to the flask, and methanol was distilled from the flask until the residue approached dryness. Then, 400 ml of anhydrous benzene was added, and distillation was continued until 200 ml of benzene was removed. The reaction mixture was freeze dried under reduced pressure, leaving a dry, white powder. The white powder was dissolved in 150 ml of dimethylsulfoxide and transferred to an addition funnel under nitrogen. The solution was added over a 60 minute period to a solution of 4-nitrobenzil (18.6 g, 0.073 mole) in dimethylsulfoxide (300 ml) and stirred at 90° C. under nitrogen. When addition was completed, the reaction mixture was stirred overnight at 23° C. and poured into a solution of sodium hydroxide (50 g) in ice water (1 liter). Extraction with toluene (3 × 50 ml) followed by chromatography on silica gel with benzene as eluent gave 15.4 g (65% yield) of 4-(3-ethynylphenoxy)benzil as a yellow oil which solidified upon standing overnight at 23° C. into a pale yellow solid (m.p. 79°-81° C.).
Analysis Calc'd for C22 H14 O3, %: C,80.97; H,4.32. Found: C,80.40; H,4.00.
A solution of 3,3'-diaminobenzidine (0.41 g, 0.0019 mole) in m-cresol (10 ml) was stirred under nitrogen at 90° C. while a previously deaerated solution of 4,4'-bis(phenylglyoxaloyl)diphenylether (0.41 g, 0.00094 mole) in m-cresol (10 ml) was added over a 10 minute period. The mixture was heated at 90°-100° C. for 2 hors and then 4-(3-ethynylphenoxy)benzil (0.69 g, 0.0021 mole) was added. After an additional hour of heating at 90°-100° C., the reaction mixture was cooled to 23° C. and poured into stirring methanol (300 ml). The yellow precipitate which formed was filtered, washed thoroughly with methanol, reprecipitated twice from tetrahydrofuran by methanol, and dried under vacuum at 60° C. to afford 0.94 g (73%) of oligomer. The structure of the oligomer was characterized by its method of preparation, NMR analysis and elemental analysis. The material softened at 145° C. and, after a 6-hour cure under nitrogen at 280° C., showed a glass transition temperature at 310° C.
The procedure of Example II was repeated, utilizing 0.42 g (0.0020 mole) of 3,3'-diaminobenzidine, 0.34 g (0.00094 mole) of 1,3-bis(phenylglyoxaloyl)benzil and 0.70 g (0.0022 mole) of 4-(3-ethynylphenoxy)benzil to afford 0.86 g (72%) of oligomer. The structure of the oligomer was characterized by its method of preparation, NMR analysis and elemental analysis. The material softened at 145° C. and, after a 6-hour cure under nitrogen at 280° C., showed a Tg at 310° C.
The procedure of Example II was repeated, utilizing 0.49 g (0.0019 mole) of 3,3'-diaminobenzidine, 0.42 g (0.00094 mole) of 4,4'-bis(phenylglyoxaloyl)diphenylsulfide, and 0.66 g (0.0020 mole) of 4-(3-ethynylphenoxy)benzil to afford 0.82 g (60%) of oligomer. The structure of the oligomer was characterized by its method of preparation, NMR analysis and elemental analysis. The material softened at 160° C. and, after a 6-hour cure under nitrogen at 280° C., showed a Tg at 309° C.
The procedure of Example II was repeated, utilizing 0.43 g (0.0020 mole) of 3,3'-diaminobenzidine, 0.53 g (0.0010 mole) of 1,3-bis(4-phenoxyphenylglyocaloyl)benzene, and 0.72 g (0.0022 mole) of 4-(3-ethynylphenoxybenzil to afford 0.87 g (57%) of oligomer. The structure of the oligomer was characterized by its method of preparation, NMR analysis and elemental analysis. The material softened at 145° C. and, after a 6-hour cure under nitrogen at 280° C., showed a Tg at 275° C.
The procedure of Example II was repeated, utilizing 0.34 g (0.0016 mole) of 3,3'-diaminobenzidine, 0.42 g (0.00082 mole) of 1,4-bis[4-phenylglyoxaloyl)phenoxy]benzene, and 0.57 g (0.0018 mole) of 4-(3-ethynylphenoxy)benzil to give 1.0 g (83% yield) of oligomer. The structure of the oligomer was characterized by the method of preparation, NMR analysis and elemental analysis. The material softened at 150° C. and, after a 6-hour cure under nitrogen at 280° C., showed a Tg at 322° C.
The procedure of Example II was repeated, utilizing 0.43 g (0.001 mole) of 4,4'-bis(phenylglyoxaloyl)diphenylether, 0.46 g (0.002 mole) of 3,3',4,4'-tetraaminodiphenylether and 0.65 g (0.002 mole) of 4-(3-ethynylphenoxy)benzil to give 1.2 g (86% yield) of oligomer. The oligomer was characterized by its method of preparation, NMR analysis and elemental analysis. The material softened at 143° C. and, after a 6-hour cure under nitrogen at 280° C., showed a TG at 298° C.
The procedure of Example II was repeated, utilizing 0.34 g (0.001 mole) of 1,3-bis(phenylglyoxaloyl)benzene, 0.46 g (0.002 mole) of 3,3',4,4'-tetraaminodiphenylether, and 0.65 g (0.002 mole) of 4-(3-ethynylphenoxy)benzil to give 1.2 g (84% yield) of oligomer. The structure of the oligomer was characterized by its method of preparation, NMR analysis and elemental analysis. The material softened at 145° C. and, after a 6-hour cure under nitrogen at 280° C., exhibited a Tg at 290° C.
The procedure of Example II was repeated, utilizing 0.52 g (0.001 mole) of 1,3-bis(4-phenoxyphenylglyoxaloyl)benzene, 0.46 g (0.002 mole) of 3,3',4,4'-tetraaminodiphenylether and 0.65 g (0.002 mole) of 4-(3-ethynylphenoxy)benzil to give 1.2 g (80% yield) of oligomer. The structure of the oligomer was characterized by its method of preparation, NMR analysis and elemental analysis. The material softened at 125° C. and, after a 6-hour cure under nitrogen at 280° C., showed a Tg at 257° C.
Properties of the cured oligomers prepared in the preceding examples are summarized in the table set forth below.
TABLE __________________________________________________________________________ Summary of Oligomer Properties ##STR6## Example Softening No. X Z Ar Pt, ° C. Tg, ° C..sup.1 __________________________________________________________________________ II .sup.2 ##STR7## ##STR8## 145 310 III ##STR9## ##STR10## 145 310 IV ##STR11## ##STR12## 160 309 ##STR13## ##STR14## 145 275 VI ##STR15## ##STR16## 150 322 VII O ##STR17## ##STR18## 143 298 VIII O ##STR19## ##STR20## 145 290 IX O ##STR21## ##STR22## 125 257 __________________________________________________________________________ .sup.1 Glass transition temperature of the cured oligomer after 6 hours a 280° C. under nitrogen atmosphere. .sup.2 Single bond.
The foregoing data demonstrate that the acetylene-terminated benzils of this invention make it possible to provide acetylene terminated phenylquinoxaline oligomers which can be cured by addition reactions in a short period of time. The curing mechanism eliminates the problem of by-product evolution so that voids are not formed in the cured products. The cured oligomers are thermally stable having a high glass transition temperature, an important property for materials which may be subjected to high temperatures.
The acetylene terminated quinoxaline compositions are very soluble in low boiling solvents, such as methylene chloride, tetrahydrofuran and dioxane. This property of the oligomers makes them eminently suitable for use in the fabrication of solvent-free prepregs and void-free structural components. The low softening points of the oligomers make it possible to employ low processing temperatures in the manufacture of structural reinforced composites. Of primary importance, the acetylenic benzils used as endcapping agents have a long shelf life, a property which makes it feasible to employ the quinoxaline compositions in a scaled-up process for fabricating composites.
As will be evident to those skilled in the art, modifications of the present invention can be made in view of the foregoing disclosure without departing from the spirit and scope of the invention.
Claims (6)
1. An acetylene terminated quinoxaline composition having the following formula: ##STR23## wherein X is a single bond, --O--, --S--, ##STR24## R is --O-- or --S--; and n is an integer ranging from 1 to 20, inclusive.
2. The composition according to claim 1 in which X is a single bond, Z is ##STR25## and R is --O--.
3. The composition according to claim 1 in which X is a single bond, Z is ##STR26## and R is --O--.
4. The composition according to claim 1 in which X is a single bond, Z is ##STR27## and R is --O--.
5. The composition according to claim 1 in which X is a single bond, Z is ##STR28## and R is --O--.
6. The composition according to claim 1 in which X is --O--, Z is ##STR29## and R is --O--.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/762,078 US4098825A (en) | 1977-01-24 | 1977-01-24 | Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/762,078 Division US4098825A (en) | 1977-01-24 | 1977-01-24 | Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US4147868A true US4147868A (en) | 1979-04-03 |
Family
ID=25064047
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/762,078 Expired - Lifetime US4098825A (en) | 1977-01-24 | 1977-01-24 | Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions |
US05/870,705 Expired - Lifetime US4147868A (en) | 1977-01-24 | 1978-01-19 | Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/762,078 Expired - Lifetime US4098825A (en) | 1977-01-24 | 1977-01-24 | Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions |
Country Status (1)
Country | Link |
---|---|
US (2) | US4098825A (en) |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4268654A (en) * | 1979-10-26 | 1981-05-19 | The United States Of America As Represented By The Secretary Of The Air Force | Acetylene terminated matrix and adhesive oligomeric compositions |
US4375536A (en) * | 1981-11-12 | 1983-03-01 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Polyphenylquinoxalines containing pendant phenylethynyl and ethynyl groups |
US4381363A (en) * | 1981-09-10 | 1983-04-26 | The United States Of America As Represented By The Secretary Of The Air Force | Cure retarding additives for acetylene-terminated polymers |
US4436886A (en) | 1982-03-09 | 1984-03-13 | The United States Of America As Represented By The Secretary Of The Air Force | 2-Phenylbanzothiazole polymers |
US4442293A (en) * | 1982-03-09 | 1984-04-10 | The United States Of America As Represented By The Secretary Of The Air Force | Di-acetylenyl-substituted 2-phenylbenzothiazoles |
EP0110465A2 (en) * | 1982-11-22 | 1984-06-13 | International Business Machines Corporation | Biphenylene end-capped quinoxaline polymers and their use as insulating coatings for semiconductor devices |
US4547592A (en) * | 1984-07-25 | 1985-10-15 | The United States Of America As Represented By The Secretary Of The Air Force | Thermosetting arylether compounds and their synthesis |
US4667002A (en) * | 1986-01-16 | 1987-05-19 | The United States Of America As Represented By The Secretary Of The Air Force | Phenylquinoxaline resin compositions |
US4683309A (en) * | 1986-01-16 | 1987-07-28 | The United States Of America As Represented By The Secretary Of The Air Force | Phenylquinoxaline resin monomers |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4731442A (en) * | 1986-10-02 | 1988-03-15 | The United States Of America As Represented By The Secretary Of The Air Force | High temperature solvent resistant amorphous thermoplastic phenylethynyl quinoxaline resin composition |
US4683340A (en) * | 1986-10-08 | 1987-07-28 | The United States Of America As Represented By The Secretary Of The Air Force | Bis(benzilyloxy) compounds |
MX2010009243A (en) * | 2008-02-28 | 2010-11-30 | Battelle Energy Alliance Llc | Thermophilic and thermoacidophilic metabolism genes and enzymes from alicyclobacillus acidocaldarius and related organisms. |
CN102212023B (en) * | 2010-04-02 | 2013-12-11 | 中国科学院化学研究所 | Thioether-containing polyphenylquinoxaline compound, and preparation method and application thereof |
CN103274917B (en) * | 2013-06-17 | 2015-06-03 | 浙江工业大学 | Method for catalyzing and synthesizing benzil derivatives from alkali type copper fluoride |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3966729A (en) * | 1975-05-19 | 1976-06-29 | The United States Of America As Represented By The Secretary Of The Air Force | Addition curable phenyl-quinoxaline compositions and their synthesis |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3340233A (en) * | 1963-07-22 | 1967-09-05 | Dow Chemical Co | Bis-vinylketo aromatic compounds and polymerization products thereof |
US3458548A (en) * | 1964-01-02 | 1969-07-29 | Monsanto Co | Metal chelates of diphenoxydibenzoylmethane |
-
1977
- 1977-01-24 US US05/762,078 patent/US4098825A/en not_active Expired - Lifetime
-
1978
- 1978-01-19 US US05/870,705 patent/US4147868A/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3966729A (en) * | 1975-05-19 | 1976-06-29 | The United States Of America As Represented By The Secretary Of The Air Force | Addition curable phenyl-quinoxaline compositions and their synthesis |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4268654A (en) * | 1979-10-26 | 1981-05-19 | The United States Of America As Represented By The Secretary Of The Air Force | Acetylene terminated matrix and adhesive oligomeric compositions |
US4381363A (en) * | 1981-09-10 | 1983-04-26 | The United States Of America As Represented By The Secretary Of The Air Force | Cure retarding additives for acetylene-terminated polymers |
US4375536A (en) * | 1981-11-12 | 1983-03-01 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Polyphenylquinoxalines containing pendant phenylethynyl and ethynyl groups |
US4436886A (en) | 1982-03-09 | 1984-03-13 | The United States Of America As Represented By The Secretary Of The Air Force | 2-Phenylbanzothiazole polymers |
US4442293A (en) * | 1982-03-09 | 1984-04-10 | The United States Of America As Represented By The Secretary Of The Air Force | Di-acetylenyl-substituted 2-phenylbenzothiazoles |
EP0110465A2 (en) * | 1982-11-22 | 1984-06-13 | International Business Machines Corporation | Biphenylene end-capped quinoxaline polymers and their use as insulating coatings for semiconductor devices |
US4507333A (en) * | 1982-11-22 | 1985-03-26 | International Business Machines Corporation | Biphenylene end-capped quinoxaline polymers and their use as insulating coatings for semiconductor devices |
EP0110465A3 (en) * | 1982-11-22 | 1987-09-09 | International Business Machines Corporation | Biphenylene end-capped quinoxaline polymers and their use as insulating coatings for semiconductor devices |
US4547592A (en) * | 1984-07-25 | 1985-10-15 | The United States Of America As Represented By The Secretary Of The Air Force | Thermosetting arylether compounds and their synthesis |
US4667002A (en) * | 1986-01-16 | 1987-05-19 | The United States Of America As Represented By The Secretary Of The Air Force | Phenylquinoxaline resin compositions |
US4683309A (en) * | 1986-01-16 | 1987-07-28 | The United States Of America As Represented By The Secretary Of The Air Force | Phenylquinoxaline resin monomers |
Also Published As
Publication number | Publication date |
---|---|
US4098825A (en) | 1978-07-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4147868A (en) | Acetylene-substituted aromatic benzils and acetylene-terminated quinoxaline compositions | |
Kovar et al. | Thermosetting acetylene‐terminated polyphenylquinoxalines | |
US4670536A (en) | Addition-curable quinoxaline resin oligomer and intermediate material for fiber-reinforced composite | |
US5155196A (en) | Polymer resulting from the cure of a preformed chromene-containing mixture | |
US4417039A (en) | Cis-enyne aromatic and aromatic heterocyclic polymers | |
US3966729A (en) | Addition curable phenyl-quinoxaline compositions and their synthesis | |
US5426234A (en) | Phenylethynyl terminated reactive oligomer | |
EP0317226A2 (en) | Aromatic compounds | |
US4400540A (en) | Oxy and thioaryl-phenylated aromatic biscyclopentadienones | |
US4978810A (en) | Polyalkenylphenol compound | |
US4513131A (en) | Thermally stable phenylacetylene terminated arylether resins | |
US3975444A (en) | Ethynyl-substituted aromatic ortho diamines and method of synthesis | |
US4005144A (en) | Ethynyl-substituted aromatic ortho diamines and method of synthesis | |
US4086232A (en) | Bis-ethynyl heterocyclic compositions and method of synthesis | |
US5670651A (en) | Thermosetting resins derived from 4-hydroxy- and 4-trimethylsiloxy-benzocyclobutene | |
US4792635A (en) | Symmetric benzophenones substituted by groups containing fluorine | |
US4547592A (en) | Thermosetting arylether compounds and their synthesis | |
US4380619A (en) | Oxy- and thioaryl-phenylated aromatic heterocyclic polymers | |
JPS6058738B2 (en) | Method for producing linear trimer of P-isopropenylphenol | |
US4764578A (en) | Compositions of polyaryloxypyridine oligomers with phthalonitrile end groups, their preparation and use for manufacturing polyaryloxypyridine co-phthalocyanine lattices | |
US4268654A (en) | Acetylene terminated matrix and adhesive oligomeric compositions | |
US4908426A (en) | Polyphenylquinoxalines via aromatic nucleophilic displacement | |
Relles et al. | Dichloromaleimide chemistry. IV. Preparation of poly (maleimide–ethers) from the reaction of bisdichloromaleimides with bisphenols | |
US5182356A (en) | Poly(1,2,4-triazole) via aromatic nucleophilic displacement | |
US4618727A (en) | Nitro substituted diphenyl ethers |